Fused-Pentagon-Configuration-Dependent Electron Transfer of Monotitanium-Encapsulated Fullerenes

We introduce monotitanium-based endohedral metallofullerenes (EMFs) using density functional theory calculations. Isomeric C₆₄ fullerenes are initially employed as hosts, and Ti@C₆₄ species show novel features on the electronic structures. Energetically, the preference of titanium residing on triple-fused-pentagon subunits is proposed in theory. More importantly, different from current knowledge on mono-EMFs, electron transfer between titanium and carbon cages is not unified but is essentially dependent on the pentagon distribution of the binding sites, giving rise to variations of the cationic titanium of Ti@C₆₄. Such selective electron-transfer character is extended to the study of the encapsulation of other neighboring metal atoms (i.e., calcium and scandium). Because of their different capabilities to accept d electrons, fullerene cages with distinct fused-pentagon motifs show selective metal encapsulation characters. In addition, some other fullerenes (C₄₄-C₄₈ and C₈₂) are selected as hosts to study the electron-transfer behavior of titanium in smaller fullerenes and larger systems without pentagon adjacency.